314478 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（1 ) 本發明係關於一個純化方法，且特別係關於一個方法， 在其中利用經加熱的氣體通過吸附劑床的方式，使吸附劑 床週期性地再生。 美國專利4 978 439提出將原料通過一個可再生之吸附劑 床，如分子篩、可以自原料中除去硫化物，且當一個床正 在進行從原料中吸附硫化物以得到產品的時候，另外一個 已經吸附了如硫醇之硫化物的吸附劑床則可以進行再生的 程序，以經加熱的氣流通過吸附劑床，使得硫化物脱附。 來自正再生之吸附劑床的流出物接著與氫反應，例如加氫 脱硫作用，將再生期間脱附之硫化物轉變成硫化氫，可於 再生氣體通過吸附劑床之前或者之後加入氫氣。自加氫脱 硫階段所得之流出物接著再通過一個適當吸收劑床，以吸 收該硫化氫。然後將得自吸收床之流出物加至產物氣流中 〇 此方法的一個缺點係需要大量的氫氣，因爲要能夠有效 地進行加氫脱硫作用，所加至再生氣體中的氫氣量，要遠 超過與硫化物反應化學計量之用量。超過之氫氣僅爲產物 流之一部份。 吾人已經設計出一個方法可以克服此缺點。本發明的方 法也係利用其他純化方法，其中可與氫氣反應之雜質化合 物係被一種可再生之吸附劑吸附。此種其他雜質之實例包 括有機金屬化合物，如有機汞和有機氯化合物。有機汞化 合物與氫氣反應會產生汞，可以適當之吸收劑，如硫化亞 銅來吸收汞。同樣地有機氯化合物與氫氣反應產生氣化氫 -4- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公嫠） (請先閱讀背面之注意事項再填寫本頁) 訂 ,Λ i—=— 第84110231號專利申請案 中文説明書修正頁(86年1月） A7 B7 n a 修正Mi. 經濟部中央標準局員工消費合作社印製 五、發明説明（2 ) ' ，可以適當之驗性吸收劑材料，如氧化銘三水化合物、竣 酸鈉或碳酸氫鈉和黏合劑之混合物所集聚而成之細粒，來 吸收氣化氫，而且混合物烺燒的溫度要低於350°C。 所以本發明提供可再生的吸附劑床之再生方法，當原料 氣流通過另一床該可再生之吸附劑，和/或通過一床不可 再生之吸收劑，以便進行脱硫得到產物氣流的時候，可再 生之吸附劑上則吸附該硫化合物，該方法包括將再生氣流 通過正在進行再生之吸附劑床，以便能使硫化合物從該吸 附劑中脱附，且將包含有該脱KL硫化合物之流出物引入一 個加氫脱硫作用催化劑中，能 <效地使得至少一部份該硫 化合物與氫氣反應，而得到硫彳Γ氫，接著以微粒狀吸收劑 吸收該硫化氫，其特徵爲用來再生的氣流在一個迴路中循 環，如此該氣流通過正進行再生的吸附劑床，然後通過該 催化劑床，再通過用以吸收硫化氫之吸收劑床，然後再回 到進行再生之吸附床，因再生氣體未加入產物氣流中，故 •在循環再生氣體中加入氫氣，以便能將氫氣之含量保持於 某一所要的程度。 本發明亦提供一個原料脱硫，得到產物氣流的方法，包 括原料通過第一個可再生之吸附劑床，因此該床可自該原 料中吸附硫化合物，原料係定期不連續地流過該第一個吸 附床，但是連續地產生該產物旅，係因爲該原料流過第 二個可再生的吸附劑床，和/或者流過一個不可再生的吸 收劑床，而同時以先前的方法再生第一個吸附劑床，且於 該第一個吸附床再生之後，原料再流過該第一個床。 -5 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ^ 裝 訂 旅 (請先閲讀背面之注意事項再填寫本頁)314478 A7 B7 Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (1) The present invention relates to a purification method, and in particular to a method in which heated gas is passed through an adsorbent bed to make The adsorbent bed is periodically regenerated. US Patent 4 978 439 proposes to pass the raw material through a renewable adsorbent bed, such as molecular sieve, to remove sulfide from the raw material, and when a bed is in the process of adsorbing sulfide from the raw material to obtain a product, the other one has The adsorbent bed of sulfide such as mercaptan can be regenerated, with a heated gas stream passing through the adsorbent bed to desorb the sulfide. The effluent from the adsorbent bed being regenerated is then reacted with hydrogen, such as hydrodesulfurization, to convert the sulfide desorbed during regeneration into hydrogen sulfide. Hydrogen can be added before or after the regeneration gas passes through the adsorbent bed. The effluent from the hydrodesulfurization stage is then passed through a suitable absorbent bed to absorb the hydrogen sulfide. The effluent from the absorption bed is then added to the product gas stream. A disadvantage of this method is that a large amount of hydrogen is required, because the amount of hydrogen added to the regeneration gas needs to exceed the amount of hydrogen that can be effectively hydrodesulfurized. Stoichiometric amount of reaction with sulfide. The excess hydrogen is only part of the product stream. We have devised a method to overcome this shortcoming. The method of the present invention also utilizes other purification methods in which impurity compounds that can react with hydrogen are adsorbed by a renewable adsorbent. Examples of such other impurities include organic metal compounds such as organic mercury and organic chlorine compounds. Organic mercury compounds react with hydrogen to produce mercury, which can be absorbed by an appropriate absorbent, such as cuprous sulfide. Similarly, organochlorine compounds react with hydrogen to produce gasified hydrogen. -4- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 public daughter) (please read the precautions on the back before filling this page). = — Amendment page for the Chinese manual of the Patent Application No. 84110231 (January 86) A7 B7 na Amendment Mi. The Central Consumer ’s Bureau of the Ministry of Economy prints the description of the invention of the employee consumer cooperative (2), which can be properly absorbed Agent materials, such as fine particles formed from a mixture of oxidized trihydrate, sodium acetate or sodium bicarbonate, and a binder, to absorb vaporized hydrogen, and the temperature at which the mixture burns should be below 350 ° C. Therefore, the present invention provides a method for regenerating a regenerable adsorbent bed. When the feed gas stream passes through the regenerable adsorbent in another bed, and / or passes through a bed of non-renewable adsorbent for desulfurization to obtain a product gas stream, The regenerated adsorbent adsorbs the sulfur compound. The method includes passing the regenerated gas stream through the regenerating adsorbent bed, so that the sulfur compound can be desorbed from the adsorbent, and the outflow containing the deKLed sulfur compound The substance is introduced into a hydrodesulfurization catalyst, which can effectively make at least a part of the sulfur compound react with hydrogen to obtain sulfur Γ hydrogen, and then absorb the hydrogen sulfide with a particulate absorbent, which is characterized by The regenerated gas stream circulates in a loop, so that the gas stream passes through the adsorbent bed being regenerated, then through the catalyst bed, then through the adsorbent bed for absorbing hydrogen sulfide, and then back to the adsorbent bed for regeneration, because The regeneration gas is not added to the product gas stream, so • Hydrogen is added to the recycled regeneration gas in order to keep the hydrogen content in a certain place Degree. The invention also provides a method for desulfurizing raw materials to obtain a product gas stream, which includes the raw materials passing through a first renewable adsorbent bed, so that the bed can adsorb sulfur compounds from the raw materials, and the raw materials flow through the first discontinuously on a regular basis Adsorption beds, but the product brigade is produced continuously because the feedstock flows through a second renewable adsorbent bed, and / or through a non-renewable absorbent bed, while simultaneously regenerating the first in the previous method Adsorbent beds, and after regeneration of the first adsorbent bed, the feedstock flows through the first bed again. -5-This paper scale is applicable to China National Standard (CNS) A4 (210X297mm) ^ Binding Brigade (Please read the notes on the back before filling this page)
1 2a 2b 3 4 5、 8 5 ί 41 0231號專利申請案 中文説明書修正頁(86年1月） 五、發明説明（3 ) 如上面所説明的’本方法可用於任何雜質上。該雜質係 a)被-個可再±之吸附劑吸㈤，b)可藉著再生氣流的方 式，自吸附劑中脱附，且〇可以和氫氣反應，得到可被微 粒狀吸收劑吸收之產物與氫氣之反應可爲還原反應、氫化 作用或者氫解作用。吸附劑和吸收劑材料、催化劑與程序 條件的選擇，當然係隨雜質本性而定，當原料中含有一個 以上之此類雜質的時候，再生迴路也要包含一個以上的催 化劑及一個以上之微粒狀吸收劑材料。爲了簡化起見，本 發明將以含硫化合物做爲雜質二做更詳盡地説明。 參考附圖以説明本發明，其f圖.1係爲傳統方法之流程 ’而圖2係根據本發明方法的流_轾。 代表原料氣體； 代表於吸附作用之可再生吸附劑床； 代表進行再生作用之可再生吸附劑床； 代表不可再生之吸附劑床； 代表旁通管； 6和7代表閥； 代表產物氣流； 9和10代表熱交換器； 1 1 代表再生氣體離開管路； 代表熱交換器；. 代表氫氣加入管路； ， 代表加氫脱硫催化劑床；、 代表吸收劑床； -6 - 本紙張尺度逋用中國國家標準（CNS ) A4規格（2丨OX297公釐） . I Ί 旅 (請先聞讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 12 13 14 15 經濟部中央標準局員工消费合作社印製1 2a 2b 3 4 5, 8 5 ί 41 0231 patent application Chinese specification amendment page (January 86) 5. Invention description (3) As described above, this method can be applied to any impurities. The impurities are a) absorbed by a resorbable adsorbent, b) can be desorbed from the adsorbent by means of regenerating airflow, and can react with hydrogen to obtain the absorbable particulate adsorbent The reaction of the product with hydrogen can be reduction, hydrogenation or hydrogenolysis. The choice of adsorbent and absorbent materials, catalysts and process conditions, of course, depends on the nature of the impurities. When the raw material contains more than one such impurity, the regeneration circuit should also contain more than one catalyst and more than one particulate. Absorbent material. For the sake of simplicity, the present invention will use a sulfur-containing compound as the impurity two for a more detailed description. The invention is described with reference to the accompanying drawings, where f. FIG. 1 is the flow of the conventional method and FIG. 2 is the flow of the method according to the invention. Represents the raw material gas; represents the renewable adsorbent bed for adsorption; represents the renewable adsorbent bed for regeneration; represents the non-renewable adsorbent bed; represents the bypass pipe; 6 and 7 represent the valve; represent the product gas flow; 9 And 10 represent the heat exchanger; 1 1 represents the regeneration gas leaving the pipeline; represents the heat exchanger;. Represents the hydrogen into the pipeline;, represents the hydrodesulfurization catalyst bed;, represents the absorbent bed; -6-this paper standard China National Standards (CNS) A4 specification (2 丨 OX297mm). I Ί brigade (please read the notes on the back before filling this page) Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 12 13 14 15 Central Ministry of Economy Printed by the Bureau of Standards and Staff Consumer Cooperative
第8411 〇231號專利申請案 中文說明書修正頁(86年丨月） 9 補充 五、發明説明（3a ) —~' 16 代表燃燒器； 17 代表探針； 1 8 代表氫氣分析器； 19 代表閥； 2 〇 代表循環器； 2 1 代表熱交換器； 22 代表分離器；及 23 代表排氣管路》 在圖1所表不的傳統方法，傷$美國專利4 978 439的方 法類似。要除去原料氣體！，例、天然氣，中的含硫化合 物，原料氣體通過一個含有適當分子篩的吸附劑床2a， I亥分子篩可以吸附原料.中的硫醇，與吸附床2&平行的是 不可再生的吸收劑床3，例如在EP 0 243 〇52中提到之細粒 氧化銅/氧化鋅/氧化鋁組合物，在一般條件下，可以有效 地吸收硫化氫。此等床2 a和3於周圍的溫度和任何適當的 壓力下’一般是在絕對壓力1至5 〇巴，例如絕對壓力2 〇 · 40巴下，很谷易操作。亦提供一個旁通管4，藉此可以迴 避床2 a和3 .。原料流過床2 a和3及流過旁通管的流速，係 利用閥5，6和7來調節，如此自床2 a和3之流出物，與通過 旁通管4之原料混合所.仔之產極^氣流8 ’可以符人押要之 硫化氫含量與總含硫化合物含量》見格》 -6 a - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） I-^--------装------ΐτ------0 (請先聞讀背面之注意事項再填寫本頁) 經濟部中央標準局負工消費合作社印製 A7 B7 五、發明説明（4 ) 例如，以體積計，典型之天然氣原料的硫化氫含量爲3_ 4 ppm，且總硫醇與其他有機硫化合物含量爲20-50 ppm， 而想要產品之規格係爲總含硫化合物少於15 ppm，且硫化 氫少於1 ppm。 當床2a正在進行吸附的時候，另一個床2b則進行再生 。可以利用部份之產品氣流8，於熱交換器9和1 〇中加熱 ’並且產品氣流8通過床2b。再生氣體經由管路11，離開 床2b，並且通過另一個熱交換器12，將其加熱至所要之 加氫脱硫作用溫度，一般係在200-400°C之範園内。然後 經由管路1 3加入氫氣。混合物通過適合之加氫脱硫催化 劑床1 4 ’該催化劑例如_酸鎳或翻酸姑。加氫脱硫作用 床1 4之流出物然後通過一個供硫化氫用之適當微粒狀吸 收劑床1 5。微細，例如細粒，之氧化鋅組合物適合用於 此床。床1 5之流出物然後做爲熱煤流過熱交換器9。熱交 換器9的部份流出物做爲燃料，且在燃燒器1 6中燃燒，以 便得到熱氣體做爲熱交換器1〇的熱煤。熱交換器9其餘的 流出物則回至產物氣流8中，之後可能需要壓縮氣體（沒 有表示出來）。於一個適當的位置，特別是如圖所表示的 ’在加風脱硫作用床14的正上流的位置，有一個探針17 連著一個氫氣分析器1 8，其依次連接到管路1 3上的閥i 9 ’以便能控制加到再生氣體中的氫氣用量。 需要熱交換器12，因爲在再生開始的時候，對於方法 中的吸附部份而言，床2b的溫度相當低：熱交換器1〇之熱 再生氣體將床2b加熱至想要的再生溫度。在加熱的期間， 本紙張尺度適用中國國家榡準（CNS ) M規格（210X297公釐） —---1------S.裝-- (請先閲讀背面之注意事項再填寫本頁) 、·!!' A7 B7 4478 五、發明説明（5 ) (請先閱讀背面之注意事項再填寫本頁) 經由管路11從床2b離開的氣體，其溫度係逐漸地增加。 當床2b的溫度高到足夠在床13發生有效的加氫脱硫作用 的時候，於氣體離開床2b前，可能有一些含硫化合物自 床2b中脱附出來。所以，在氣體進行加氫脱硫作用之前 ，需要多一個熱交換器〗2來加熱經由管路"離開床。的 氣體。床2b的溫度最好在範圍250-3 5(TC内，才能有效地 使再生完全。 多於兩個床2a和2b是比較好的。因此其他的床可以準 備再生，或者預備進行吸附，或者可以進行冷卻，將溫度 由再生的溫度冷卻至進行吸附所需的溫度。如果可以接受 產品中有一些含硫化合物的話，那麼正在冷卻的吸附床也 可以進行吸附：因此當吸附床正在冷卻的時候，可能必須 停止吸附’或者減少氣體的流量’氣體流經旁通管4。 經濟部中央標準局員工消費合作社印裝 令人振奮的是，在某些情況下，當正在進行再生的時候 ，不必一定要有可再生的吸附劑床進行吸附。因此，當可 再生的吸附劑床正在進行再生的時候，在某些情況下，原 料通過不可再生的吸收劑床，可能可以獲得可接受之產物 。而於其他情況下，沒有必要利用不可再生的吸收劑床： 在此情況下’可以利用二個或以上的可再生之吸附劑床， 如此當另一個正在進行再生的時候，還有一個可以進行吸 附。 此方式冼程中的一個缺點係爲，爲了能夠得到加氫脱硫 作的滿意效果，經由管路I3所添加的氫氣量，遠超過化 學計量所需要的用量，所以部份過量氫氣的做爲加熱熱交 -8- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） A7 B7 五、發明説明（6 ) 換器1 0之氣體的一部份，同時其餘的氫氣流進產品氣流8 之中。 在圖2的流程中’參考數字的意義與圖i相同。於此具 體實施例中，係描述本發明，利用循環氣流來使得床2 a 再生。在熱交換器9中加熱從循環器2〇出來的再生氣流， 且於該再生氣流流過床2b進行再生之前，再於熱交換器 1 〇中加熱。經由管路1 1流出之床2 b的流出物，亦必須在 熱交換器12中加熱’且經由管路13加入氫氣。混合物接 著流過加氫脱硫作用之催化床1 4，微粒狀的硫化氫吸收 劑床15，然後做爲熱父換器9的熱煤。離開熱交換器9之 氣體接著在熱交換器2 1中冷卻，以便能使得水蒸氣凝 結，然後在分離器2 2中分離得到液體水。此水係在再生 的過程，從床2b所脱附的水，和在床15中硫化氫與硫化 氫吸收劑反應所得到的水。從分離器所得的氣體再次循環 回到循環器2 0。在一個適當的位置定期地進行排氣，該 位置係在床15和床2b氣體流向之間。於圖2中，管路23 所表示的即爲此項排氣。此種排氣可爲連續式的或者間歇 式的，可以做爲在燃燒器16中燃燒之部份燃料，提供加 熱熱交換器10的熱氣體。燃燒器16其餘之燃料係來自原 料氣流或者產物氣流8，如圖2所示。 在圖2的具體實施例中看到，再生氣體在一個迴路中循 環。在圖1的具體實施例中，從熱交換器9得之經純化的 再生氣體係回到產物氣流8中，同時部份產物氣流做爲在 熱交換器9中加熱之新鮮再生氣體。如圖1所表示，因 nn nn · I- (束-- (請先閱讀背面之注意事項再填寫本頁)Amendment Page of Chinese Specification for Patent Application No. 8411 〇231 (January 86) 9 Supplement V. Description of Invention (3a) — 16 ′ stands for burner; 17 stands for probe; 1 8 stands for hydrogen analyzer; 19 stands for valve 2 represents a circulator; 2 1 represents a heat exchanger; 22 represents a separator; and 23 represents an exhaust line. The conventional method shown in FIG. 1 is similar to the method of US Patent 4,978,439. To remove the raw gas! , Examples, natural gas, sulfur compounds, raw material gas through an adsorbent bed 2a containing an appropriate molecular sieve, I Hai molecular sieve can adsorb the raw material. Mercaptan, parallel to the adsorption bed 2 & is a non-renewable absorbent bed 3. For example, the fine-grained copper oxide / zinc oxide / alumina composition mentioned in EP 0 243 〇52 can effectively absorb hydrogen sulfide under general conditions. These beds 2 a and 3 are generally easy to operate at ambient temperature and any appropriate pressure, usually at an absolute pressure of 1 to 50 bar, for example at an absolute pressure of 20.4 bar. A bypass pipe 4 is also provided, whereby the beds 2 a and 3 can be avoided. The flow rate of the raw material flowing through the bed 2 a and 3 and through the bypass pipe is regulated by valves 5, 6 and 7, so that the effluent from the bed 2 a and 3 is mixed with the raw material passing through the bypass pipe 4. Aberdeen's production line ^ Airflow 8 'The hydrogen sulfide content and the total sulfur compound content that can be stipulated by the people "see the grid" -6 a-This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) I- ^ -------- Installed ------ Ιτ ------ 0 (please read the precautions on the back before filling in this page) Printed A7 by the Consumer Labor Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs B7 5. Description of the invention (4) For example, by volume, the typical natural gas raw material has a hydrogen sulfide content of 3-4 ppm, and the total mercaptan and other organic sulfur compounds content is 20-50 ppm. It is less than 15 ppm total sulfur compounds and less than 1 ppm hydrogen sulfide. While bed 2a is undergoing adsorption, another bed 2b is undergoing regeneration. Part of the product gas stream 8 can be used to heat the heat exchangers 9 and 10 and the product gas stream 8 passes through the bed 2b. The regeneration gas leaves the bed 2b via line 11 and passes through another heat exchanger 12 to heat it to the desired hydrodesulfurization temperature, generally within a range of 200-400 ° C. Then hydrogen is added via line 13. The mixture passes through a bed 14 of suitable hydrodesulfurization catalyst. The catalyst is, for example, nickel acid or acid. The effluent from hydrodesulfurization bed 14 then passes through a bed 15 of suitable particulate absorbent for hydrogen sulfide. Fine, for example, fine-grained zinc oxide compositions are suitable for this bed. The effluent from bed 15 is then passed through heat exchanger 9 as hot coal. Part of the effluent from the heat exchanger 9 is used as fuel and burned in the burner 16 to obtain hot coal as hot coal for the heat exchanger 10. The remaining effluent from the heat exchanger 9 is returned to the product gas stream 8, after which compressed gas may be required (not shown). At a suitable position, especially as shown in the figure, 'in the position upstream of the desulfurization desulfurization bed 14, there is a probe 17 connected to a hydrogen analyzer 18, which in turn is connected to the pipeline 13 The valve i 9 'in order to be able to control the amount of hydrogen added to the regeneration gas. The heat exchanger 12 is needed because at the beginning of regeneration, the temperature of the bed 2b is relatively low for the adsorption part of the process: the heat of the heat exchanger 10 regenerates the bed 2b to the desired regeneration temperature. During the heating period, the paper size is applicable to China National Standard (CNS) M specification (210X297mm) ---- 1 ------ S. Packing-(Please read the precautions on the back before filling in this Page), · !! 'A7 B7 4478 V. Description of the invention (5) (Please read the notes on the back before filling in this page) The temperature of the gas leaving the bed 2b via line 11 gradually increases. When the temperature of bed 2b is high enough to effect effective hydrodesulfurization in bed 13, some sulfur-containing compounds may be desorbed from bed 2b before the gas leaves bed 2b. Therefore, before the gas undergoes hydrodesulfurization, an additional heat exchanger 2 is required to heat the exit bed via the pipeline. gas. The temperature of the bed 2b is preferably in the range of 250-3 5 (TC, in order to effectively complete the regeneration. More than two beds 2a and 2b is better. Therefore other beds can be prepared for regeneration, or prepared for adsorption, or It can be cooled, cooling the temperature from the regeneration temperature to the temperature required for adsorption. If there are some sulfur-containing compounds in the product, the adsorption bed that is being cooled can also be adsorbed: therefore when the adsorption bed is cooling It may be necessary to stop the adsorption or reduce the flow of gas. The gas flows through the bypass pipe. 4. The printing of the consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs is exciting. In some cases, when regeneration is in progress, it is not necessary There must be a regenerable adsorbent bed for adsorption. Therefore, when the regenerable adsorbent bed is undergoing regeneration, in some cases, the raw material may pass through the non-renewable adsorbent bed, and an acceptable product may be obtained. In other cases, it is not necessary to use non-renewable absorbent beds: in this case, two or more Renewable adsorbent bed, so that when another is being regenerated, there is another one that can be adsorbed. One disadvantage of this method in the process is that in order to obtain a satisfactory effect of hydrodesulfurization, it is added via line I3 The amount of hydrogen gas far exceeds the amount required for stoichiometry, so some of the excess hydrogen is used for heating and heat transfer. -8- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) A7 B7 5. Invention Description (6) A part of the gas in the converter 10, while the remaining hydrogen flows into the product gas stream 8. In the process of FIG. 2, the meaning of the reference numerals is the same as that of FIG. I. In this specific embodiment, In the description of the present invention, the recycle gas stream is used to regenerate the bed 2a. The regeneration gas stream from the circulator 20 is heated in the heat exchanger 9 and before the regeneration gas stream flows through the bed 2b for regeneration, the heat exchanger 1 〇 heating. The effluent of bed 2 b flowing out through line 11 must also be heated in heat exchanger 12 and hydrogen is added through line 13. The mixture then flows through the catalysis of hydrodesulfurization 1. A bed 15 of particulate hydrogen sulfide absorbent, which is then used as the hot coal of the heat exchanger 9. The gas leaving the heat exchanger 9 is then cooled in the heat exchanger 21 to allow water vapor to condense, and then Liquid water is separated in separator 22. This water system is the water desorbed from bed 2b during the regeneration process, and the water obtained by reacting hydrogen sulfide with hydrogen sulfide absorbent in bed 15. From the separator The gas is circulated back to the circulator 20 again. The exhaust is periodically performed at an appropriate position between the gas flow of the bed 15 and the bed 2b. In FIG. 2, the pipeline 23 represents this for This type of exhaust can be continuous or intermittent, and can be used as part of the fuel burned in the burner 16 to provide hot gas for heating the heat exchanger 10. The remaining fuel for the burner 16 comes from the raw gas stream or product gas stream 8, as shown in FIG. It is seen in the specific embodiment of Fig. 2 that the regeneration gas circulates in a circuit. In the specific embodiment of FIG. 1, the purified regeneration gas system obtained from the heat exchanger 9 is returned to the product gas stream 8, and part of the product gas stream is used as the fresh regeneration gas heated in the heat exchanger 9. As shown in Figure 1, due to nn nn · I- (beam-(please read the notes on the back before filling this page)
、1T 經濟部中央標準局貝工消費合作社印製 -9- 014478 A7 B7 五、發明説明（7 ) 在熱交換9之經純化的再生氣體返回之後，可以從產物氣 流中任一點得到新鮮的再生氣體，所以與循環系統相同。 然而在圖1的具體實施例中，在從產物氣體中取得新鮮之 再生氣體之前，從吸附劑床2 a和吸收劑床3中得到的產物 氣體加到經純化之再生氣體中。因爲通常新鮮的再生氣體 僅佔產物氣體的一小部份，所以大部份的再生氣體不會循 環，同時在其中過量的氫氣就流到產物氣流中。根據本發 明之圖2具體實施例中，在再生氣體循環之前，並沒有於 其中加入產物氣體，因此過量的氣體循環使用（除了氫氣 做爲部份排氣2 3排除之外）。結果經由管路1 3所添加之氫 氣量，與從床2 b脱附之含硫化合物的加氫脱硫作用所需 之化學計量接近。 在再生迴路中，可以在床2 b的周遭提供一個由閥所控 制回流管路，如此當沒有吸附床正在進行再生的時候，可 以維持再生氣體循環，且/或進入加氫脱硫作用催化劑之 氣流中含硫化合物的濃度。 經濟部中央標準局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) 有多於吸附床2 a和2 b之吸附床係爲比較好的。因此其 他的吸附床可以準備再生，或者預備進行吸附，或者可以 進行冷卻，從再生的溫度降爲吸附所需的溫度。如果產品 中能夠接受少量含硫化合物的話，正在進行冷卻的吸附床 也可以進行吸附：因此當吸附床正在冷卻的時候，必須停 止吸附，或減少氣體的流量，氣體流經旁通管4。 此外，當正在進行再生的時候，在某些情況下，也不需 要有一個可再生的吸附劑床進行再生。因此，當可再生的 -10- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 314478 A7 B7 經濟部中央標準扃員工消費合作社印製 五、發明説明（8 ) 吸附劑床正在進行再生的時候，於某些情沉下，只要原料 通過不可再生的吸收劑床就有可能得到可以接受的產物了 。而在其他情況下，可能不需要不可再生的吸收劑床：在 這情況下，利用二個或者以上的可再生之吸附劑床，如此 當其中一個正在進行再生的時候，另一個可進行吸附。 實例如下，處理含有35 ppm之硫化物之天然氣原料，其 速率爲每小時120000牛頓平方米（Nm3/hr)，經計算知需要 12000牛頓平方米/小時的再生氣體。進入加氫脱硫作用催 化床的再生氣體中之尖峰硫化物含量，一般以體積計約爲 1 % ’而且需要大量的氫氣，才能有效地進行加氫脱硫作 用’而在圖1的流程中，大部份的氫氣都浪費掉了，也就 是説氫氣不是用於加氫脱硫的步驟中，而僅是產物氣流的 一部份。在採用本發明的時候，過量的氫氣則循環再利用 。據估算在本發明方法中所需要添加的氫氣量，一般約爲 圖1流程中所需用量之4 %。 再生所採用的氣體可爲產物氣流的一部份，或者可爲任 何一種適當的氣體，例如天然氣或者氮氣。再生迴路在任 何適當的壓力下都可作用，不過通常爲能夠進行吸附的壓 力。進行再生的吸附床不必爲分子篩，但是可爲任何可再 生之吸附劑，且該吸附劑能夠吸附雜質化合物。 (請先聞讀背面之注意事項再填寫本頁) 、βτ -11 - 本紙張尺度適财闕家縣（CNS ) A4脉（2H)X297公酱）、 1T Printed by Beigong Consumer Cooperative of Central Bureau of Standards, Ministry of Economic Affairs-9-014478 A7 B7 V. Description of the invention (7) After the purified regeneration gas from the heat exchange 9 is returned, fresh regeneration can be obtained from any point in the product gas stream Gas, so it is the same as the circulation system. However, in the specific embodiment of Fig. 1, the product gas obtained from the adsorbent bed 2a and the adsorbent bed 3 is added to the purified regeneration gas before the fresh regeneration gas is obtained from the product gas. Since fresh regeneration gas usually only accounts for a small part of the product gas, most of the regeneration gas does not circulate, and at the same time excess hydrogen flows into the product gas stream. According to the specific embodiment of FIG. 2 of the present invention, no product gas is added to the regeneration gas before it is circulated, so excess gas is recycled (except that hydrogen is excluded as part of the exhaust gas 23). As a result, the amount of hydrogen gas added via line 13 is close to the stoichiometry required for the hydrodesulfurization of the sulfur-containing compounds desorbed from bed 2b. In the regeneration circuit, a return line controlled by a valve can be provided around the bed 2b, so that when no adsorption bed is being regenerated, the regeneration gas circulation can be maintained and / or enter the hydrodesulfurization catalyst gas flow The concentration of sulfur compounds in the medium. Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). It is better to have more than 2 a and 2 b. Therefore, other adsorption beds can be prepared for regeneration, or prepared for adsorption, or can be cooled to reduce the temperature from regeneration to the temperature required for adsorption. If a small amount of sulfur-containing compounds can be accepted in the product, the adsorption bed that is being cooled can also be adsorbed: therefore, when the adsorption bed is cooling, the adsorption must be stopped, or the gas flow must be reduced, and the gas flows through the bypass pipe 4. In addition, when regeneration is in progress, in some cases, it is not necessary to have a renewable adsorbent bed for regeneration. Therefore, when the renewable -10- this paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 314478 A7 B7 Central Standard of the Ministry of Economic Affairs Printed by the Employee Consumer Cooperative Fifth, the description of the invention (8) When regenerating, it sinks in certain circumstances, as long as the raw material passes through a non-renewable absorbent bed, it is possible to obtain an acceptable product. In other cases, a non-renewable absorbent bed may not be needed: in this case, two or more renewable adsorbent beds are used, so that when one of them is undergoing regeneration, the other can be adsorbed. An example is as follows. A natural gas feed containing 35 ppm of sulfide is processed at a rate of 120,000 Newton square meters per hour (Nm3 / hr). It is calculated that 12,000 Newton square meters per hour of regeneration gas is required. The peak sulfide content in the regeneration gas entering the hydrodesulfurization catalyst bed is generally about 1% by volume 'and a large amount of hydrogen is required to effectively perform hydrodesulfurization'. In the process of Figure 1, the large Part of the hydrogen is wasted, which means that the hydrogen is not used in the hydrodesulfurization step, but only a part of the product gas stream. When using the present invention, the excess hydrogen is recycled. It is estimated that the amount of hydrogen to be added in the method of the present invention is generally about 4% of the amount required in the process of FIG. The gas used for regeneration may be part of the product gas stream, or may be any suitable gas, such as natural gas or nitrogen. The regeneration circuit can work at any suitable pressure, but it is usually a pressure that allows adsorption. The adsorbent bed for regeneration need not be a molecular sieve, but can be any regenerable adsorbent, and the adsorbent can adsorb impurity compounds. (Please read the precautions on the back before filling out this page), βτ -11-The size of this paper is suitable for Quejia County (CNS) A4 vein (2H) X297 male sauce)